Intermediate partial oxidation product and method of making same



Jan. 1, 192 9.

J. H. JAMEs INTERMEIS'IATE PARTIAL OXIDATION PRODUCT. AND METHOD OFMAKING was Original Filed Jan. 22,, 1919 Patented Jan. 1, 1929.

UNITED STATES JOSEPH HIDY JAMES, 01E PITTSBURGH, PENNSYLVANIA, ASSIGNORBYRNES, TRUSTEE, OF SEWICKLEY, PENNSYLVANIA.

INTERMEDIATE PARTIAL OXIDATION PRODUCT AND METHOD OF MAKING Continuationof application Serial No. 272,567, filed January 22, 1919. Thisapplication filed March 7,

1919, Serial No. 281,124.

The figure is a sectional side elevation, showing one form of apparatusfor carrying out my invention.

My invention relates to a partial oxida 5 tion product and method ofmaking the same, and forms a continuation of my copending application,Serial No. 272,567, filed January 22, 1919, which was a continuation inpart of my then pending application, Serial No. 132,569, filed November21, 1916. In those applications I disclosed a liquid partial oxidationproduct having a plural-- ity of different hydrocarbons containingartificially-introduced chemically-combined oxygen. I also disclosed apartial oxidation process wherein a mixture of carbon-hydrogen-oxygencontaining constituents in gaseous phase, and more particularly ahydrocarbon-oxygen mixture in gaseous phase, was passed in contact witha catalyst at an elevated temperature below that of continuousself-sustained combustion, and preferably below a red heat. Thehydrocarbon employed was preferably a mineral oil, such as one of thedistillates of petroleum, although the process might be applied to crudeoil or oils from shales or their distillatcs. or oils from lowtemperature distillation of lignites or coals, or other distillates. Idisclosed the vaporizing of such oils, forming a heated mixture of theoil vapor with a measured proportion of air, either with or withoutsteam. and passing the heated mixture in contact with a suitablecatalyst while keeping the reaction below that of continuousself-sustained combustion, thereby producing a mixture of valuableintermediate oxidation products in the range from alcohol to oxygenatedorganic acids, and could hold the reaction temperature within the properrange by maintaining proper conditions.

In such process, while heat is continuously supplied to vaporize theoil, and, if neces- HIT). additional heat is supplied to bring themixture to the reacting temperature, especially in starting; yet thecatalyst is kept below a red heat and preferably below a' heat whichshows any glow, to prevent continuous self-sustained combustion whichwould consume a large amount of the hydrocarbon. The heat might risetemporarily to a point of ignition, but in such case the yield is re-Renewed August 4, 1926.

be changed to prevent a continuance of such combustion.

If steam is added,-it will serve as a diluent to hold down the reactionzone temperature,

and Will also aid in vaporizing heavier oils. The amount of steam-shouldbe carefully regulate.

Bylong experimenting I have found that a number of inter-dependingvariable conditlons or factors dependent on each other are important inobtaining proper yields. Thus, the proportion of air, theparticularcatalyst used, the velocity of the current or steam, and thetemperature maintained in the reaction zone are inter-dependent andshould be accordingly varied in relation to each other. The thickness ofcatalyst is also a factor. The air ratio should be maintained preferablyabove the theoretical amount to give the desired intermediate oxidationproducts, but below that for complete combustion; and at such a ratethat continuous selfsustained combustion does not occur. The reactiongives out heat and the temperature should be held down inthe conversionzone. The variable factors may be inter-adjusted to give a productwherein other intermediate oxidation products predominate over anyorganic acids produced, and the hydrocarbon may be mixed withoxygen oran oxygencontaining gas in formingthe gaseous phase mixture. In making apredominance of bodies other than acids, the temperature is preferablysomewhat lower than where a larger percentage of acids is desired.

The range of temperature for carrying out my invention extends, so faras I have determined, from about 230 C. up to 450500 C. The temperatureused will depend somewhat upon the particular hydrocarbon be ingtreated, from gasoline to the heaviest hydrocarbons that can bevaporized; and also depends somewhat onthe particular catalyst used, theproportion of air or oxygen employed, whether or not steam is added, andto some extent, on the speed of the current 100 or stream mixture. Ihave found that the lighter the hydrocarbon treated, the higher thereaction zone temperature should be maintained; and accordingly, whenheavier distillates are used, lower temperatures may 195 be employed.

The catalysts hereinafter described differ in activity. With an activecatalyst kept at the highest temperature consistent with a highcommercial yield, the proportion of air may be kept at or above thatrequired by theory for the products desired, the temperature, of course,being kept below that where products of complete combustion, namely,carbonic dioxide and water, form to a large extent. With more activecatalysts a higher speed may be used, especially where a highertemperature within the desirable range is employed. The time of contactwith the catalyst may be lessened when a more active catalyst and ahigher temperature are used. Vith hydrocarbons of greater molecularweight more heat must be applied to vaporize them, but the reaction zoneheat should be lower than otherwise. \Vith hydrocarbons of lessmolecular weight, less heat will vaporize them, but the temperature ofthe reaction zone should be higher within the desirable range. \Vithfractions of widely different molecular weight the difference inreaction zone temperature is rather marked.

The desired temperature in the reaction zone can be kept down below aglowing temperature by lowering the proportion of air nearer thetheoretical amount as the temperature rises, and by raising theproportion of air as the temperature decreases, within certain limits.

The products after leaving the reaction zone are either cooled andcondensed, or absorbed for recovery.

The catalyst, when used, is preferably arranged in a layer or successionof layers, and preferably consists of the oxides or compounds of metalshaving more than one valence, such, for example, as blue oxides ofmolybdenum or the oxides of vanadium or uranium.

The products of this method are condensed by reducing the temperature ofthe outlet ases and products, and also preferably by bringing them incontact with a liquid such as water, giving mixtures of partialoxidation products usually ranging from alcohols through aldehydes toaldehyde fatty acids.

The process can be varied by varying the factors of temperature,proportions of mixture, speed of flow, amount of diluent, etc., toeither give a preponderance of products short of acids or apreponderance of acids. The present divisional case is intended to coverthe-new product wherein the other intermediate oxidation productspreponderate over the acids, as well as that form of the method whichproduces such a product.

For example, by keeping the reaction zone temperature below a red heatand below that which produces a preponderance of acids, I can produce incommercial quantities a mixture of valuable oxidation products,including aldehydcs and alcohols, and can hold the reaction temperaturewithin the preferred range by regulating the external heat applied forvaporizing the liquid hydrocarbon or hydrocarbon derivative when inliquid form, or otherwise maintaining proper conditions.

If steam is added it will serve as a diluent to hold down the reactionzone temperature and will also aid in vaporizing heavier hydrocarbons.The steam should be carefully regulated and when properly used will aidin increasing the yield. The proportion of air, the particular catalystused, the temperature maintained, and other factors are inter-dependentand should be accordingly varied in proper relation to each other underthe conditions of each material treated and the products desired. Heatmay be continuously supplied to vaporize the oil, and the air ratio ispreferably maintained somewhat above the theoretical amount for theproducts desired. The reaction gives out heat and the temperature shouldbe held down in the conversion zone.

As regards the catalyst, I prefer to employ the complex oxides orcompounds of metals having a varying valence. All parts of the complexmay consist of oxides of the same metal or of different metals. Forexample, an excellent catalyst in this connection consists of the blueoxides of molybdenum which contain molybdenyl-molybdenate andmolybdenyl-molybdenite, and are probably all chemical compounds of twoor more oxides of molybdenum representing different states of oxidation.These complexes may be regarded as salts,i. e., compounds of one or morebasic oxides with one or more acid oxides. Other complexes of value forsuch catalysts are chromie chromate, tungsten tungstate, the manganesecomplexes, the vanadium complexes, etc.

The basic and acid parts of these complexes may be formed from oxides ofdifferent metals, in which case each metal or group of metals usedshould possess varying "alence. Examples, of this class are: uranylmolybdate, uranyl molybdite, cobalt molybdate, cobalt molybdite, uranylvanadate, uranyl vanadite, etc.

The metals, whose oxide complexes I prefer to employ as the acid part ofthe catalyst. since I have found them to be of high activity in thisfield, are the metals of high melting point electrouegativclow-atomicvolume metals having an atomic weight above 40. These metalsappear on the Lothar ltleyer diagram of the periodic series beginning onthe descending side of the third peak. descending side of thefourth peakand the descending side of further peaks developed since the date ofthis diagram. The class includes the following metals: titanium,vanadium, chromium, manganese, zirconium, niobium, molybdenum, tantalum,tungsten Cir and uranium. The basic oxides may be the lower oxides ofthese metals or may be the oxides of iron, copper, nickel, lanthanum,cobalt, thorium and the eight ornine rare earth metals.

In both acid or basic portions there may,

of course, be two or more of these combined.

The conditions will 'vary somewhat, dcpending upon the particularcatalyst employed. Some catalysts tend to produce more acids and othercatalysts tend toproduce more intermediate oxidation products short ofacids.

\Vith the above description of the conditions, which are varied in orderto give the best commercial results according to the interaction of thefactors described, I will now describe one form of apparatus for car:rying out my invention.

In the drawings, 2 represents a valved air pipe through which air issupplied under pressure 3 a meter for the air, and 4 the pipe leadingfrom the meter into a heating and mixing vessel 5. 6 represents a vesselcontaining liquid hydrocarbon and 7 a valved pipe leading therefrom intothe mixing vessel 5. 8 indicates a burner having a valved supply pipe 9,by which the heat may be regulated. 10 represents the walls of-thefurnace or heating chamber in which the retort or mixing vessel 5 isset, the heated mixture of hydrocarbon vapor and air passing from themixing vessel through the channel 11 to the catalytic screen 12. Thiscatalytic screen is shown as having a frame 12 clamped or bolted betweenthe ends of the channel 11 and the flanged end ofthe conduit 13, leadingto a vertical condenser 14. The products emerging from the catalyticscreen pass down through the tubes 15 of the condenser into the vessel16. 17 represents the valved inlet pipe for water passing into thecondenser, and 18 the outlet pipe for the circulating water. The vessel16 is provided With an outlet 19 for fumes, 20 being the valved pipe bywhich the condenser products are drawn off. Between the condenser andthe vessel 16 and the furnace I preferably provide an insulating screen21 of some heat insulator to keep the heat of the furnace away from thecondensing apparatus.

22 represents a pyrometer which is preferably in the form of an electriccouple with its wires 23 leading to an external temperature indicator24.

As the heated mixture of vapor and air in the proper proportions passesthrough the catalytic screen under the regulated temperature referredto, partial oxidation or partial combustion takes place, the productsbeing immediately taken to and through the condenser, and the desiredproduct collecting in the vessel succeeding the condenser. Thecondensing apparatus may, of course, be

eter. The oil used was a gas oil fraction distilling from 250 to 295degrees C. The air rate was two liters per minute or 1.6 times thetheoretical amount required for aldehyde fatty acid formation. Theabsorbers consisted of eight water bubblers. The oil was fed at the rateof 126 cubic centimeters per hour. The time of contact with the catalystwas .32 seconds; the temperature of the catalyst was maintained atabout270 degrees (3.; the duration of the run was one hour and'35 minutes. Atest of the exit gas showed 24% of carbon dioxide and 1% of oxygen. 150

cubic centimeters of liquid oxidation products i were recovered, ofwhichabout 45% by volume consisted of oxygenated organic acids and about55% of other products in the range from alcohols to acids, includingunchanged hydrocarbons.

(2) The catalyst consisted of uranyl uranate and uranyl uranite onasbestos 1.25 centimeters thick and 4.4 centimeters in diameter. The oilused was kerosene distilling at 250 to' 295 C. The air rate was 4 litersper minute, the condensing and absorbing system consisting of two wormcondensers and four water bubblers. The oil was fed in at" the rate of200 cubic centimeters per hour.

The time of contact was about .33 second.

The temperature of the catalyst was maintained at about 310 C. ,Theduration of the run was 33 minutes. As a result, 76 cubic centimeters ofliquid product were recovered, which, on analysis, gave about 70% ofaldehydes (aldehyde-like bodies) and about 30% of aldehyde fatty acids,there being some alcohols present.

Vith an apparatus for larger-scale operation, practically identical withthe drawing accompanying this specification, the following run wasmade:'

Conditions.

and 324 degrees C. i The distillate had a specific gravity'of .8125 at20 .degrees C.

(0) Air rate: about 216 cubic feet per hour.

(J) Absorbing system: no scrubbers, only the parallel tube condenser asshown in ligure.

(6) Oil feed: 2.5 gallons per hour.

Time of contact of h. c. vapor-air mix ture with catalyst: approximatelysecond. (g) Temperature of catalyst: 310 to 320 degrees C.

(it) Total time consumed in run: 2 hours.

Results.

(a) Carbon dioxide analysis (by volume) in exit gas stream during run:((3%, 1.0%, .s%).

Carbon monoxide analysis (by volume) in exit gas stream during run:(6.8% 8%).

(b) 3.7 gallons of product (having specific gravity at 20 degrees C. of.852) were recovered which had the following analysis: aldehyde fattyacids, 46% by volume, aldehyde 28%, leaving undetermined 26% by volume.

Actual recovery of aldehyde acids, by weight, based on weight ofhydrocarbon mixture treated: 50.7%.

The above examples in connection with the description of the apparatusand operation will snfliciently disclose to those skilled in chemistrythe essentials of the process, under the conditions recited above.

So far as I have found, the lowest reacting temperature for successfulcommercial operation can be used when the catalyzer consists of theintermediate complex compounds of oxides of molybdenum. The next lowesttemperature has been used with a catalyst consisting of the compounds ofmolybdenum with other metallic oxides of the group above named.

A catalytic layer is important'in producing commercial yields, althougha non-catalytic screen may be used, or even a plain tube to surround thereaction zone, with lower percentages of yield.

The resulting material containing partial oxidation products short ofacids and of different molecular weights may be used in the industries,or the product, or a part thereof, may be further oxidized; as, forexample, by again passing it through the process.

I have also obtained a preponderance of bodies short of acids, includingaldehyde-like bodies, using the blue oxides of molybdenum as a catalyst,and a. temperature of about 230 to 250 C., the air rate being about 1.6times the theoretical amount required for producing such products.

By the words mineral hydrocarbons in the claims. I intend to includecrude mineral oil or shale oil. or their distillates, products orderivatives including hydrocarbon gas whether wet or dry, or theproducts or derivatives from low temperature distillation of lignites orcoals. The oils or distillates, or products thereof, may vary, somehaving a paraflin base and some having an asphaltum base. Such oilscontain saturated straight chain or branched chain aliphatichydrocarbons, and may also contain unsaturated straight chain orbranched chain hydrocarbons, such as those of the olefin type and thoseof the acetylene type. They may also contain some aromatic or othercyclic hydrocarbons with side chains, the latter being saturated orunsaturated, and also naphthenes.

Many changes may be made in the material treated in the apparatus, thevarious conditions, etc., without departing from my invention, since Iconsider myself the first to discover a practicableprocess wherebyhydrocarbons may be converted by vapor or gas phase partial oxidationinto a product having a preponderance of partial oxidation productsshort of acids.

By the terms aldehyde fatty acids and aldehyde acids herein, I intend toinclude such forms of oxygenated organic acids as are produced by mypartial oxidation methods from hydrocarbons or hydrocarbon products orderivatives in th form of gases or liquids, and the exact character andform of which are not now fully known.

The claims herein are intended to cover my broad partial oxidationprocess and product, and also the process and product in the specieswherein the oxidation products short of acids and the other hydrocarbonspresent predominate over and are in excess of the acids produced. Myapplication, Serial No. 272,567, will contain the species wherein acidspredominate and other specific features not herein claimed.

I claim:

1. As a new article of manufacture, a liquid partial oxidation productcontaining organic acids of the fatty acid type and a materialproportion of intermediate oxidation products, the oxidation productsshort of aldehyde fatty acids being in excess of said acids.

2. As a new article of manufacture, a liquid partial oxidation productcontaining organic acids of the fatty acid type and a. materialpro-portion of intermediate oxidation products, the oxidation productsshort of aldehyde fatty acids being of different molecular weights andbeing in excess of said acids.

3. As a new article of manufacture,a liquid gaseous phase partialoxidation product containing a material proportion of aliphaticaldehydes of ditierent molecular weights, the oxidized bodies short oforganic acids being in predominance.

4. As anew article of manufacture, a liquid partial oxidation productcontaining aldehyde-like bodies and aldehyde fatty acids, the formerbeing in excess of the latter.

5. As a new article of manufacture, a liquid partial oxidation productcontaining a material proportion of aliphatic intermediate oxidationproducts, those products short of acids being in excess of any organicacids.

6. As a new article of manufacture, a liquid partial oxidation productcontaining aliphatic aldehydes, aldehyde fatty acids and unconvertedhydrocarbons, the aldehydes and unconverted hydrocarbons being in excessof the aldehyde fatty acids.

7. As a new article of manufacture, a liquid gaseous phase partialoxidation product containing a plurality of aliphatic aldehydelikebodies in material proportion, the oxidized bodies short of organicacids being in predominance.

8. The process of making aldehyde-like bodies. consisting in passing aheated mixture of mineral hydrocarbon and air through a hot reactionzone, and maintaining the zone temperature and the air ratio below thatof continuous self-sustained combustion and below that at which aldehydeacids predominate.

9. In the process of making aliphatic aldehydes, the steps consisting ofpassing a mixture of finely divided hydrocarbons and air through a hotreaction zone at a temperature below. red heat and Within the rangewhere the aldehydes in the product predominate over the acids produced.

10. In the process of making aliphatic aldehyde-like bodies, the stepsconsisting in passing a heated mixture of hydrocarbon vapor and air overa catalyst containing a compound of a metal of high-melting-pointelectronegative low-atomic volume at a temperature below red heat andwithin the range Where the aldehyde-like bodies in the prod; uctpredominate over aldehyde fatty acids.

11. In the manufacture of a liquid partial oxidation product having aplurality of different hydrocarbons containing. artificiallyintroducedchemically-combined oxygen, the steps consisting of forming agaseous-phase mixture of aliphatic hydrocarbon and oxygen, passing themixture over a catalyst at a temperature below a red heat, andinteradjusting the variable factors in the range where otherintermediate oxidation products predominate over any acids produced.

12. In the manufacture of a liquid partial oxidation product having aplurality of different hydrocarbons containing artificiallyintroducedchemically-combined oxygen, the steps consisting of forming agaseous-phase mixture of aliphatic hydrocarbon and oxygen, passing themixture through a hot reaction zone at a temperature below a red heat,and interadjusting the variable factors in the range where otherintermediate oxidation "products predominate over any acids produced.

13. In the manufacture of a liquid partial oxidation product having aplurality of different hydrocarbons containing artificiallying pointelectro-negat-ive low-atomic volume at a temperature below'a redheat,and interadjusting the variable factors in the range where otherintermediate oxidation products predominate over any acids produced.

15. In the manufacture of a liquid partial oxidation product having aplurality of different hydrocarbons containing artificiallyintroducedchemically-combined oxygen, the

steps consisting of forming a gaseous-phase mixture of aliphatichydrocarbon and oxygen, passing the mixture over a catalyst at atemperature below a red heat, and maintaining the temperature and theoxygen ratio below that of continuous self-sustained combustion andwithin the range wherein other intermediate oxidation productspredominate over any acids produced.

16. The process of synthetically forming an aliphatic liquid partialoxidation product containing a predominance of intermediate oxidationproducts short of acids, con sisting of passinga mixture ofcarbon-hydrogen-oxygen containing constituents in gaseous phase incontact with a catalyst at an elevated temperature below a red heat andat a pressure less than 5 atmospheres.

17. The process of. synthetically forming an aliphatic liquid partialoxidation product containing a .predominance of intermediate oxidationproducts short of acids, consisting of passing a mixture ofcarbon-hydrogenoxygen containing constituents in gaseous phase incontact with a catalyst containing compounds of at least two differentgroups of the periodic series other than the alkali metal group.

18. The process of synthetically forming an aliphatic liquid'partialoxidation product containing a predominance of intermediateoxidationproducts short of acids, consisting of passinga mixture ofcarbon-hydrogenoxygen containing constituents in gaseous phase incontact With a catalyst containing compounds of at least two differentgroups of the periodic series other than the alkali metal group at anelevated temperature below a red heat and at a pressure less than 5atmospheres. j

19. In the manufacture of a partial oxidation product containing apredominance of intermediate oxidation products short of acids. thesteps consisting of forming a gaseous-phase mixture of hydrocarbon andoxygen, passing the mixture over a catalyst at a temperature below thatof continuous selfsustained combustion. and interadjusting the variablefactors to produce unconsumed oxygen in the tail gas and give a productwherein other intermediate oxidation products predominate ovcr any acidsproduced.

20. In the manufacture of a partial oxidation product containing apredominance of intermediate oxidation products short of acids, thesteps consisting of formii'ig a gaseous-phase mixture of aliphatichydrocarlmn and oxygen. passing the mixture over a catalyst at atemperature below that of continuous self-sustained combustion,interadjusting the variable factors in the range wherein otherintermediate oxidation products predominate over any acids produced, andcollecting water soluble products in a water solution.

21. In the process of synthetically forming an aliphatic liquid partialoxidation product containing a predominance of intermediate oxidationproducts other than acids, the steps consisting of passing a mixture ofcarbon-hydrogen-oxygen containing constituents in gaseous phase incontact with a catalyst containing compounds of a plurality of metals,one of which belongs to the highmelting-point electroncgatirelow-atomicrolume class.

22. In the process of synthetically forming an aliphatic liquid partialoxidation product containing a predominance of intermediateoxidationproducts other than acids, the steps consisting of passing a mixture ofcarbon-hydrogen-oxygen containing constituents ingaseous phase incontact with a catalyst containing compounds of a plurality of metals,two of which belong to the high-melting-point elcctronegativelow-atomic-volume class.

23. In the process of synthetically forniing a liquid partial oxidationproduct containing a predominance of intermediate oxidation productsother than acids, the steps consist-- ing of passing a mixture ofaliphatic hydrocarbon and oxygen containing constituents in gaseousphase in contact with a catalyst containing compounds of a plurality ofmetals, one of which belongs to the high-meltingpoint electronegativelow-atomic-volume class.

2-1. In the process of synthetically forming a liquid partial oxidationproduct containing a predominance of intermediate oxidation productsother than acids, the steps consisting of passing a mixture of aliphatichydrocarbon and oxygen containing constituents in gaseous phase incontact with a catalyst containing compounds of a plurality of metals.two of which belong to the high-melting-point electronegativc low-atomicvolume class.

25. In the process of synthetically forming a liquid partial oxidationproduct containing a. predominance of intermediate oxidation productsother than acids, the steps consisting of passing a mixture of aliphatichydrocarbon and oxygen containing constituents in gaseous phase incontact with a catalyst containing compounds of a pluralit of metals,one of which belongs to the lighmelting-point electronegative low-atomicvolume class, at an elevated temperature below a red heat.

26. In the process of synthetically forming an aliphatic liquid partialoxidation product containing a predominance of intermediate oxidationproducts other than acids, the steps consisting of passing a mixture ofcarbonhydrogen-oxygen containing constituents in 'gaseous phase incontact with a catalyst containing compounds of a plurality of metals,one of which belongs to the high-meltingpoint electronegativelow-at-omic-volume class, and condensing the products both indirectlyand by direct contact with a liquid. 27. In the process of syntheticallyforming an aliphatic liquid partial oxidation product containing apredominance of intermediate oxidation products other than acids, thesteps consisting of passing a mixture of hydrocarbon and. oxygencontaining constituents in gaseous phase in contact with a catalystcontaining compounds of a plurality of metals, one of which belongs tothe high-melting point electroncgative low-atomic volume class. andcondensing the products both indirectly and by direct contact with aliquid.

28. In the process of making intermediate oxidation products containinga predominance of products other than acids, the steps consisting ofpassing a gaseous mixture of aliphatic hydrocarbon and oxygen containingconstituents through a. hot reaction zone at a temperature below that ofcontinuous self-sustained combustion and interadjusting the variablefactors to give a product wherein other intermediate oxidation productspredominate over any acids produced.

29. In the process of making intermediate oxidation products containinga predominance of products other than acids, the steps consisting ofpassing a gaseous mixture of aliphatic hydrocarbon and oxygen containingconstituents through a hot reaction zone at a temperature below that ofcontinuous selfsustained combustion and interadjusting the variablefactors to produce unconsumed oxygen in the tail gas and give a productwherein other intermediate oxidation products predominate over any acidsproduced.

30. In the process of making partial oxidation products by partialcombustion, the steps consisting of passing a mixtureof minlltl ,that ofcontinuous sclfsustained combustion and within the partial combustionrange.

In the process of making partial combustion products, the stepsconsisting of mixing finely divided mineral oil with air in measuredamounts, passing the mixture in contact with a catalyst and maintainingthe atalystat a. temperature below a red heat.

34. In the process of making partial combustion products. the stepsconsisting of vaporizing mineral oil by applying external heat to avessel containing the oil, mixing oxygen and a diluent in measuredamounts with the hot vapor, and passing the preheated mixture through avheated conversion zone at a temperature below red heat and'within theintermediate oxidation range for the mix.- ture used.

35. In the process of making partial combustion products, the stepsconsisting of Vaporizing mineral oil by applying external heat to avessel containing the oil, mixing oxygen and a diluent in measuredamounts with the hot vapor and passing the mixture through a catalyst,and maintaining the cata- 13 st at a temperature below a red heat.

36. In the process of making partial combustion products, the stepsconsisting vaporizing mineral oil by applying external heat to a vesselcontaining the oil, mixing oxygen and a diluent in measured amounts withthe hot vapor and passing the mixture through a catalyst, andmaintaining the catalyst at a temperature below a red heat byregulating.

the amount of external heat applied for Vaporizing the oil.

37. In the process of making partial combustion products, the stepsconsisting of passing a heated mixture of mineral oil vapor and airthrough a hot reaction zone and maintaining the zone temperature and theair ratio below that of continuous self-sustained combustion and withinthe intermediate oxidation range for the mixture used.

38. In the process of making partial combustion products, the stepsconsisting of feeding mineral oil to a container, applying external heatto the container to vaporize the oil, feeding regulated amounts of air,forming a heated mixture of the oil vapor and air, passing the heatedmixture through a catalyst, indicating the temperature of the cata- 4lytic zone, and regulating said catalytic zone temperature.

39. In the process of making partial combustion products, the stepsconsisting of feeding mineral oil, applying external heat andcontinuously vaporizing the oil, feeding regulated amounts of air,forming. a heated mixture of the oil vapor and air, passing the .heatedmixture through a catalyst, indicating the temperature of the catalyticzone, and regulating said catalytic zone temperature by regulating theamount. of external heat applied in vaporizing the oil.

40. In the process of making partial combustion products, the stepsconsisting of passing a mixture of mineral oil vapor and air through acatalyst at a temperature below a red heat.

41 In the process of making partial combustlon products, the stepsconsisting of passing a mixture of heated mineral oil vapor,

air and a diluent through a hot reaction zone at atemperature below ared heat.

42. In the process of making'partial combustion products, the stepsconsisting of passing a mixture of mineral oil vapor and air through aheated reaction zone at a,temperature between 230 C. and about450 0.,and condensing and recovering a material per centage of intermediatecombustion products. 43. In the process of making partial combustionproducts, the steps consisting in passmg a mixture of mineral oil vapor,air and a diluent through a heated reaction zone at a maintainedtemperature of between 230 C. and 450 C., and condensing and recoveringa material percentage of intermediate combustion products.

44. In the process of making partial combustion products, the stepsconsisting of passing a heated mixture of mineral oil vapor and airthrough a catalyst containing a compoundof a metal of high meltingpoint, electro-negative low-atomic volume at a temperature below that ofcontinuous self-sustained combustion.

45. In the process of making partial combustion products, the-stepsconsisting in passing a mixture of mineral oil vapor and air through acatalyst containing the complex compounds of-metal of electronegativelowatomic volume having a varying valence at a temperature below that ofcontinuous self sustained combustion. 46. In the process of makingpartial combustion products, the steps consisting of mixing finelydivided mineral oil with air in measured amounts, passing the mixture incontact with a catalyst, and maintaining the catalyst at a temperaturebelow a red heat and within the range where aldehyde fatty acidspredominate over aldehydes in the product.

47. As a new article of manufacture, a liquid gaseous-phase partialoxidation product containing a material proportion of aliphaticaldehydes of difi'erent molecular weights.

48. As a new article of manufacture, a liquid gaseous-phase partialoxidation product containing aplurality of aliphatic aldehyde-likebodies in a material proportion.

49. As a new article of manufacture, a liquid gaseous-phase partialoxidation product containing, a material proportion of aliphaticaldehydes and aldehyde fatty acids.

50. In the process of catalytic oxidation of petroleum hydrocarbons thestep which comprises passing the reaction mixture ofpetroleum vapor andair over a catalytic mass maintained at a black heat just below a lowred heat.

51. In the catalytic oxidation of petroleum oils the step whichcomprises passing a mixture of petroleum vapor and'air over a compositecaltalyst containing two active oxidizing agents maintained at a blackheat approaching red heat,

52. In the manufacture of a liquid partial oxidation product, the stepsconsisting of forming a gaseous-phase mixture of aliphatic hydrocarbonand oxygen and passing the mixture through a hot reaction zone at atemperature below that of continuous self-sustained combustion.

53. In the manufacture of a liquid partial oxidation product, the stepsconsisting of forming a gaseous phase mixture of aliphatic hydrocarbonand oxygen and passing the mixture through a hot reaction zone at atemperature below a red heat.

54. In the manufacture of liquid partial oxidation products the stepsconsisting of forming a gaseous-phase mixture of aliphatic hydrocarbonand oxygen and passing the mixture over a catalyst at a temperaturebelow that of continuous self-sustained combustion. .55. In themanufacture of liquid partial oxidation products the steps consisting offorming a gaseous-phase mixture of aliphatic hydrocarbon and oxygen andpassing the mixture over a catalyst at a temperature below a red heat. 7

56. In the manufacture of liquid partial oxidation products the stepsconsisting of forming a gaseous-phase mixture of aliphatic hydrocarbonand oxygen and passing the mixture over acatalyst containing a com poundof a high melting point electronegative low-zitomicwolume metal at atemperature below that of continuous self-sustained combustion.

In testimony whereof I have hereunto set my hand.

JOSEPH HIDY JAMES.

